EP0610818A1 - Méthode pour préparer une résine de silicone - Google Patents
Méthode pour préparer une résine de silicone Download PDFInfo
- Publication number
- EP0610818A1 EP0610818A1 EP94101676A EP94101676A EP0610818A1 EP 0610818 A1 EP0610818 A1 EP 0610818A1 EP 94101676 A EP94101676 A EP 94101676A EP 94101676 A EP94101676 A EP 94101676A EP 0610818 A1 EP0610818 A1 EP 0610818A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alcohol
- silicone resin
- component
- methyl
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920002050 silicone resin Polymers 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 alkyl silicate Chemical compound 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 230000007062 hydrolysis Effects 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 6
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical group C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- BPMGYFSWCJZSBA-UHFFFAOYSA-N C[SiH](C)O[SiH3] Chemical compound C[SiH](C)O[SiH3] BPMGYFSWCJZSBA-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- SCTQCPWFWDWNTC-UHFFFAOYSA-N diphenylsilyloxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[SiH](C=1C=CC=CC=1)O[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 SCTQCPWFWDWNTC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003759 ester based solvent Substances 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims description 2
- XOGRRUJDOGRPLB-UHFFFAOYSA-N ethyl-[ethyl(methyl)silyl]oxy-methylsilane Chemical compound CC[SiH](C)O[SiH](C)CC XOGRRUJDOGRPLB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 239000005453 ketone based solvent Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- IWICDTXLJDCAMR-UHFFFAOYSA-N trihydroxy(propan-2-yloxy)silane Chemical compound CC(C)O[Si](O)(O)O IWICDTXLJDCAMR-UHFFFAOYSA-N 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- RMZSTOAGUSEJFY-UHFFFAOYSA-N methyl-[methyl(phenyl)silyl]oxy-phenylsilane Chemical compound C=1C=CC=CC=1[SiH](C)O[SiH](C)C1=CC=CC=C1 RMZSTOAGUSEJFY-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 31
- 238000009833 condensation Methods 0.000 abstract description 8
- 230000005494 condensation Effects 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 238000002955 isolation Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001879 gelation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005191 phase separation Methods 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 229910020485 SiO4/2 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 150000004762 orthosilicates Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
Definitions
- the present invention relates to a method for the preparation of a silicone resin composed of monofunctional siloxane units (M units) and tetrafunctional siloxane units (Q units) which has a high molecular-weight and an excellent storage stability.
- Silicone resins composed of monofunctional (M) and tetrafunctional (Q) siloxane units are used as starting materials for pressure-sensitive adhesives, as reinforcing components for silicone rubber compositions, and as starting materials for film-forming materials such as silicone varnishes.
- Methods proposed for the preparation of there resins include: (a) cohydrolysis by the addition of water to a mixture of alkyl silicate and hydrolyzable trialkylsilane (US-A 2,857,356), and (b) dripping alkyl silicate into a mixed system of organosilicon compound(s) (selected from disiloxanes and hydrolyzable triorganosilanes) in aqueous hydrochloric acid solution (Japanese Patent Publication [Kokai] 3-60851 [60,851/1991]).
- a silicone resin should have a high molecular-weight.
- high molecular-weight silicone resin is prepared by the methods taught in the above documents either the product undergoes gelation or it has a very poor storage stability in solution form.
- the silicone resin is subsequently isolated with an organic solvent that is poorly soluble in water and which has a dielectric constant of at least 4.
- the method of the present invention produces a high molecular-weight silicone resin that has excellent storage stability in solution form.
- the process comprises the hydrolysis and condensation of (A) a disiloxane and (B) an alkyl silicate in (C) an aqueous solution that contains an alcohol and an inorganic acid followed by isolation of the resin with (D) an organic solvent.
- Component (A) in the present invention is the source of the monofunctional siloxane unit (M unit) in the silicone resin product.
- This disiloxane has the following general formula: [R12HSi]2O R1 in this formula is a monovalent hydrocarbon group. It is exemplified by alkyl groups such as methyl, ethyl, propyl, butyl and pentyl; aryl groups such as phenyl, tolyl, xylyl and naphthyl; and aralkyl groups such as benzyl and phenethyl. The methyl group is preferred.
- the disiloxane comprising component (A) can be 1,1,3,3-tetramethyldisiloxane, 1,3-dimethyl-1,3-diethyldisiloxane, 1,1-dimethyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, 1,3-dimethy1-1,3-diphenyldisiloxane and mixtures of two or more of the preceding.
- Component (B) is the source of the tetrafunctional siloxane unit (Q unit) in the silicone resin product.
- This alkyl silicate has the following general formula: Si(OR2)4 R2 in the preceding formula represents alkyl groups. They are exemplified by methyl, ethyl, and propyl. The methyl group is preferred due to ease of acquisition and because the hydrolysis rate of component (B) increases as the number of carbons in the alkyl group declines.
- the alkyl silicates of component (B) are available commercially as orthosilicates.
- Component (B) can be selected from methyl orthosilicate, ethyl orthosilicate, and isopropyl orthosilicate.
- Methyl orthosilicate and ethyl orthosilicate are preferred due to ease of acquisition and because the hydrolysis rate increases with diminishing number of carbons in the alkyl group in the alkyl silicate.
- this ratio of (A)/(B) falls below 0.05, high molecular weight silicone resin can be obtained but gelation also readily occurs. While gelation of the silicone resin product is inhibited at ratios in excess of 0.6, the silicone resin obtained will have a low molecular weight and poor film-forming properties.
- the preparative method of the present invention begins with the cohydrolysis/condensation of the aforementioned components (A) and (B) in aqueous solution (component (C) which contains at least 30 wt% alcohol and at least 5 wt% inorganic acid.
- component (C) which contains at least 30 wt% alcohol and at least 5 wt% inorganic acid.
- the preparative method of the present invention moderates the hydrolysis and condensation rate of component (B) and thereby prevents an increase in molecular weight of the silicone resin product to the point of gelation.
- ком ⁇ онент (C) There are no particular restrictions on the alcohols useable in the aqueous solution comprising component (C). Operable alcohols are methyl alcohol, ethyl alcohol, isopropyl alcohol, and n-propyl alcohol. Methyl alcohol and ethyl alcohol are preferred because lower boiling points facilitate post-synthesis solvent replacement by component (D) of the silicone resin.
- Component (C) must contain at least 30 wt% alcohol.
- An alcohol content of less than 30 wt% fails to moderate the hydrolysis and condensation rate of component (B) during the reaction between components (A) and (B) and, therefore, cannot prevent an increase in molecular weight by the silicone resin product to the point of gelation.
- aqueous solution comprising component (C) may also contain water-soluble organic solvents insofar as the object of the present invention is not impaired.
- the inorganic acid used in the aqueous solution comprising component (C) is exemplified by hydrochloric acid, sulfuric acid, and nitric acid. Hydrochloric acid is preferred because it can be easily removed from the silicone resin reaction mixture after synthesis of the silicone resin.
- Component (C) must contain at least 5 wt% inorganic acid.
- An inorganic acid content below 5 wt% results in a slow component (A) cleavage during the reaction between components (A) and (B). This results in the preferential development of the hydrolysis and condensation of component (B) and, thus, an increase in molecular weight to the point of gelation.
- component (C) used in the method of the present invention is not specifically restricted.
- Component (C) is preferably added in a quantity that makes possible a thorough hydrolysis and condensation of component (B).
- reaction temperature is also not specifically restricted in the present invention, but the reaction temperature preferably does not exceed 30°C and more preferably does not exceed 15°C.
- a characteristic feature of the present invention is that the silicone resin afforded by the hydrolysis and condensation reaction is separated using organic solvent (component (D)) which is poorly soluble in water and which has a dielectric constant of at least 4.
- component (D) organic solvent
- the basis for this feature is that the presence of inorganic acid in the silicone resin product results in a deterioration of the storage stability of the silicone resin and causes corrosion of treated surfaces when the silicone resin is employed as a coating agent.
- Inorganic acid impurities can be removed from the silicone resin by thoroughly dissolving the silicone resin from the reaction mixture into component (D) and washing with water.
- the organic solvent comprising component (D) must be poorly soluble in water, i.e., it must form two layers with water.
- component (D) is not specifically restricted.
- a mixture of components (C) and (D) may first be prepared, and components (A) and (B) then reacted in such a system.
- components (A) and (B) may first be reacted in component (C), and component (D) then immediately added to the resulting system.
- the thorough dissolution from the reaction system of the high molecular-weight silicone resin product is made possible by the fact that the organic solvent comprising component (D) has a dielectric constant of at least 4 and is, therefore, highly polar.
- drying of the solution affords an additional improvement in the solution storage stability.
- component (D) is not specifically restricted in the preparative method of the present invention.
- Component (D) is preferably added in a quantity that can thoroughly dissolve the silicone resin that is produced.
- the silicone resin product preferably is a high molecular-weight silicone resin with a number-average molecular-weight of at least 3,000.
- the high molecular weight and excellent film-forming properties of the silicone resin afforded by the present invention enable its application as a silicone resin coating, as an additive for silicone rubber compositions, and as an additive for silicone varnishes.
- reaction solution was colorless and transparent. 100 mL methyl isobutyl ketone and then 100 mL water were added to the reaction solution, whereupon phase-separation occured into two layers. The lower layer was taken off and shaken out with 50 mL of additional methyl isobutyl ketone. After phase-separatio, the upper layer was collected and combined with the water-containing upper layer from the reaction solution. 200 mL water was added to this and the system was shaken. Because this yielded an emulsion, 200 mL diethyl ether was added. Quiescence then resulted in a further phase-separation.
- the concentrate was dripped onto a silicon wafer and the solvent was evaporated by standing in air at room temperature to produce a film with a thickness of approximately 1 micrometer.
- This film was subjected to transmission mode-based structural analysis using a Fourier-transform infrared spectrochemical analyzer (FTIR).
- FTIR Fourier-transform infrared spectrochemical analyzer
- reaction solution was stirred for an additional 15 minutes while cooling with ice. It was then stirred for 4 hours at room temperature.
- the reaction solution was colorless and transparent. 100 mL methyl isobutyl ketone and then 100 mL water were added to the reaction solution, whereupon phase-separation occurred into two layers. The lower layer was taken off and shaken out with 50 more mL of methyl isobutyl ketone. After phase-separation, the upper layer was collected and combined with the water-containing upper layer from the reaction solution. 200 mL water was added to this and the system was shaken. Because this yielded an emulsion, 100 mL diethyl ether was added.
- This solution was subjected to GPC, and the dissolved component was thereby determined to have a number-average molecular-weight of 3,310, a weight-average molecular-weight of 5,760, and a dispersity of 1.74 (Mw/Mn).
- the dissolved component was determined by NMR analysis to be silicone resin with the following structural formula: [H(CH3)2SiO 1/2 ] 0.5 [SiO 4/2 ] 1.0 .
- the concentrate was dripped onto a silicon wafer and the solvent was evaporated by standing in air at room temperature to produce a film with a thickness of approximately 1 micrometer.
- This film was subjected to transmission mode-based structural analysis using a FTIR analyser.
- a broad, strong absorption peak assigned to the siloxane bond was observed in the region of 1100 cm ⁇ 1
- a sharp, strong absorption peak assigned to the Si-CH3 group was observed in the region of 1260 cm ⁇ 1
- a sharp, strong absorption peak assigned to the SiH group was observed in the region of 2150 cm ⁇ 1
- a sharp, medium absorption peak assigned to the C-H group was observed in the region of 2960 cm ⁇ 1.
- reaction was stirred for an additional 15 minutes while cooling with ice. It was then stirred for 4 hours at room temperature.
- the reaction solution was an emulsion at this point. When the system was subsequently held at room temperature while purging with nitrogen, the reaction solution gelled within 12 hours.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP04458993A JP3153373B2 (ja) | 1993-02-09 | 1993-02-09 | シリコーンレジンの製造方法 |
JP44589/93 | 1993-02-09 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0610818A1 true EP0610818A1 (fr) | 1994-08-17 |
EP0610818B1 EP0610818B1 (fr) | 1997-06-11 |
Family
ID=12695669
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94101676A Expired - Lifetime EP0610818B1 (fr) | 1993-02-09 | 1994-02-04 | Méthode pour préparer une résine de silicone |
Country Status (6)
Country | Link |
---|---|
US (1) | US5338817A (fr) |
EP (1) | EP0610818B1 (fr) |
JP (1) | JP3153373B2 (fr) |
KR (1) | KR100282990B1 (fr) |
DE (1) | DE69403689T2 (fr) |
TW (1) | TW238321B (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0725103A2 (fr) * | 1995-02-02 | 1996-08-07 | DOW CORNING ASIA, Ltd. | Résines de silicone thérmodurcissables |
DE19800021A1 (de) * | 1998-01-02 | 1999-07-08 | Huels Silicone Gmbh | Verfahren zur Herstellung von Polyorganosiloxanharzen, die mono- und tetrafunktionelle Einheiten enthalten |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10292047A (ja) * | 1997-04-21 | 1998-11-04 | Toray Dow Corning Silicone Co Ltd | シロキサン化合物の製造方法 |
DE102008041601A1 (de) | 2008-08-27 | 2010-03-04 | Evonik Goldschmidt Gmbh | Verfahren zur Herstellung verzweigter SiH-funtioneller Polysiloxane und deren Verwendung zur Herstellung flüssiger, SiC- oder SiOC-verknüpfter, verzweigter organomodifizierter Polysiloxane |
DE102011087931A1 (de) * | 2011-12-07 | 2013-06-13 | Wacker Chemie Ag | Herstellung hochmolekularer Siliconharze |
JP6277974B2 (ja) * | 2015-02-26 | 2018-02-14 | 信越化学工業株式会社 | 付加硬化性シリコーン樹脂組成物及び光半導体装置用ダイアタッチ材 |
JP6702224B2 (ja) * | 2017-02-17 | 2020-05-27 | 信越化学工業株式会社 | 付加硬化性シリコーン樹脂組成物及び光半導体装置用ダイアタッチ材 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0195936A1 (fr) * | 1985-02-22 | 1986-10-01 | Toray Silicone Company Limited | Procédé de préparation de polyorganosiloxanes et les polymères préparés par ce procédé |
EP0389138A2 (fr) * | 1989-03-22 | 1990-09-26 | Dow Corning Limited | Procédé de préparation de résines de siloxane |
JPH0360851A (ja) * | 1989-07-31 | 1991-03-15 | Nippon Steel Corp | セラミックス製の溶湯ノズルとその支承装置 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1017883B (de) * | 1954-07-08 | 1957-10-17 | Fellows Gear Shaper Co | Schalt- und Vorschubeinrichtung fuer Zahnradherstellungsmaschinen |
-
1993
- 1993-02-09 JP JP04458993A patent/JP3153373B2/ja not_active Expired - Fee Related
- 1993-11-22 TW TW082109805A patent/TW238321B/zh active
- 1993-11-23 US US08/155,894 patent/US5338817A/en not_active Expired - Fee Related
-
1994
- 1994-02-04 DE DE69403689T patent/DE69403689T2/de not_active Expired - Fee Related
- 1994-02-04 EP EP94101676A patent/EP0610818B1/fr not_active Expired - Lifetime
- 1994-02-07 KR KR1019940002218A patent/KR100282990B1/ko not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0195936A1 (fr) * | 1985-02-22 | 1986-10-01 | Toray Silicone Company Limited | Procédé de préparation de polyorganosiloxanes et les polymères préparés par ce procédé |
EP0389138A2 (fr) * | 1989-03-22 | 1990-09-26 | Dow Corning Limited | Procédé de préparation de résines de siloxane |
JPH0360851A (ja) * | 1989-07-31 | 1991-03-15 | Nippon Steel Corp | セラミックス製の溶湯ノズルとその支承装置 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0725103A2 (fr) * | 1995-02-02 | 1996-08-07 | DOW CORNING ASIA, Ltd. | Résines de silicone thérmodurcissables |
EP0725103A3 (fr) * | 1995-02-02 | 1997-07-16 | Dow Corning Asia Ltd | Résines de silicone thérmodurcissables |
DE19800021A1 (de) * | 1998-01-02 | 1999-07-08 | Huels Silicone Gmbh | Verfahren zur Herstellung von Polyorganosiloxanharzen, die mono- und tetrafunktionelle Einheiten enthalten |
US6197914B1 (en) | 1998-01-02 | 2001-03-06 | Wacker Chemie Gmbh | Method for preparing polyorganosiloxane resins that contain mono-and tetrafunctional units |
Also Published As
Publication number | Publication date |
---|---|
KR100282990B1 (ko) | 2001-03-02 |
EP0610818B1 (fr) | 1997-06-11 |
US5338817A (en) | 1994-08-16 |
TW238321B (fr) | 1995-01-11 |
DE69403689D1 (de) | 1997-07-17 |
JPH06234857A (ja) | 1994-08-23 |
JP3153373B2 (ja) | 2001-04-09 |
DE69403689T2 (de) | 1998-01-08 |
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